(1) (1)200424158 玖、發明說明 【發明所屬之技術領域】 本發明係關於一種從三級丁醇/水混合物中分離2 一丁 醇（下文中也可表示爲二級丁醇或SBA )的方法，該三級 丁醇/水混合物係從三級丁醇（T B A )(特別地是由工業 用c 4 一烴混合物中製得之三級丁醇）解離成異丁烯與水 的反應中獲得。 【先前技術】 異丁燒係丁基橡膠、聚異丁燒、異丁嫌寡聚物、支鏈 C5 —醛類及C5 —羧酸類的製造原料。彼同時也可用做爲 烷基化劑及製備過氧化物之中間物。 在工業用股流中，異丁烯會伴隨者飽和與不飽和C4 -烴而一起存在。由於在異丁烯與1 -丁烯之間有著很小 的沸點差異或非常低的分離因子，因此，異丁燒無法藉由 蒸餾而很有經濟效益地從這些混合物中分離。所以，異丁 烯之離析是藉由將之轉化爲可輕易從殘留之烴混合物中分 離的衍生物，然後將該離析出之衍生物再解離成異丁烯及 衍生物形成物質。 通常，可利用下列程序以便從C4餾份，如蒸汽裂化 裝置之C4餾份中分離異丁烯。待大部份多數之不飽和烴 (主要是丁二烯）已藉由萃取（或萃取性蒸餾）除去或選 擇性氫化成直鏈丁烯後’再將殘留混合物（提餘液I或氫 化裂化之C4 )與醇或水反應。若使用甲醇時可獲得甲基 4 (2) (2)200424158 第三一 丁基醚（ΜIB E )，使用水時可獲得三級丁醇（ TB A )。待彼等析出後，此二者產物便可依其生成的逆轉 形式再解離以形成異丁烯。 TBA之解離反應比MIBE之解離更易於操作，且只會 得到較小量之副產物，因而是離析異丁條的較佳方法。 TB A之解離較佳地係在酸存在下於氣相或液相中以部份轉 化TBA之方式來進行。 若是使用含異丁烯之烴股流（其中存在著直鏈丁烯） 來製備TBA，則會形成少量的2 -丁醇（SBA )。 此舉是否存在著任何進一步的問題，端視如何處理所 得之反應混合物以獲得純TB A或TBA/水共沸混合物。由 於反應混合物中有低含量之2 -丁醇，所以在TB A或 TBA/水共沸混合物中2— 丁醇的最大容許量應不超過0.2 質量％。 然而，若工業用TB A或TBA/水共沸混合物已部份解 離爲異丁烯及水時，若分離出所生成之異丁烯將會導致 TBA/水共沸混合物富含2 — 丁醇（SBA )。若不將2 —丁 醇分開，則此混合物就不適於用來製備商品化品質之TB A 或TBA/水共沸混合物。同樣地，欲從此混合物中製備異 丁烯也變得不實際，此乃因爲增多的2 -丁醇含量會使異 丁烯中之直鏈丁烯濃度增加，如此異丁烯的規格就無法達 成。所以，必需要排出部份的2 —丁醇，同時也要避免 TBA的損失。(1) (1) 200424158 发明. Description of the invention [Technical field to which the invention belongs] The present invention relates to a method for separating 2 monobutanol from a tertiary butanol / water mixture (hereinafter may also be expressed as secondary butanol or SBA ) Method, the tertiary butanol / water mixture is dissociated from tertiary butanol (TBA) (especially tertiary butanol prepared from industrial c 4 hydrocarbon mixture) into isobutene and water. obtain. [Prior technology] Isobutylene-based butyl rubber, polyisobutylene, isobutylene oligomer, branched chain C5-aldehydes and C5-carboxylic acids are the raw materials for manufacturing. They can also be used as alkylating agents and intermediates for the preparation of peroxides. In industrial streams, isobutene is accompanied by saturated and unsaturated C4-hydrocarbons. Due to the small difference in boiling points between isobutene and 1-butene or very low separation factors, isobutene cannot be economically separated from these mixtures by distillation. Therefore, isobutene is isolated by converting it into a derivative that can be easily separated from the remaining hydrocarbon mixture, and then dissociating the isolated derivative into isobutene and a derivative-forming substance. In general, the following procedure can be used to separate isobutene from a C4 cut, such as the C4 cut of a steam cracker. After most of the unsaturated hydrocarbons (mainly butadiene) have been removed by extraction (or extractive distillation) or selectively hydrogenated to linear butenes, the residual mixture (raffinate I or hydrocracking) C4) reacts with alcohol or water. If methanol is used, methyl 4 (2) (2) 200424158 tertiary butyl ether (MIB E) can be obtained, and when using water, tertiary butanol (TB A) can be obtained. After their precipitation, the two products can be dissociated according to their reversed forms to form isobutene. The dissociation reaction of TBA is easier to operate than the dissociation of MIBE, and only a small amount of by-products can be obtained, so it is a better method for isolating diisobutene. The dissociation of TB A is preferably carried out by partially converting TBA in the gas or liquid phase in the presence of an acid. If TBA is produced using isobutene-containing hydrocarbon streams, where linear butene is present, a small amount of 2-butanol (SBA) is formed. Are there any further issues with this, depending on how the resulting reaction mixture is processed to obtain a pure TBA or TBA / water azeotrope. Due to the low content of 2-butanol in the reaction mixture, the maximum allowable amount of 2-butanol in the TBA or TBA / water azeotropic mixture should not exceed 0.2% by mass. However, if the industrial TBA or TBA / water azeotrope has been partially dissociated into isobutene and water, the separation of the isobutene produced will result in the TBA / water azeotrope being rich in 2-butanol (SBA). Without 2-butanol separation, this mixture is not suitable for the preparation of commercial quality TBA or TBA / water azeotropic mixtures. Similarly, it is impractical to prepare isobutene from this mixture, because the increased 2-butanol content will increase the concentration of linear butene in isobutene, so the isobutene specification cannot be achieved. Therefore, some 2-butanol must be discharged, and the loss of TBA must be avoided.
因此，本發明之目標係提供一種可從含有SB A、TB A (3) (3)200424158 及水的混合物中分離SBA且不會發生TBA損失之方法。 然而，此三組份之SBA ' TBA及水的混合物卻難以 經由蒸餾分離’因爲此三組份系統顯現出蒸鶴分界線’其 連接了在約 1 1重量％水（文獻報告是在大氣壓下1 0至 1 2.5重量％ )之二成份的水/TB A共沸混合物（圖1中之B 點），及在約2 8重量％水（文獻報告是在大氣壓下2 6 · 7 至3 2重量％ )之二成份的水/ S B A共沸混合物（圖1中之 C點）。此蒸餾分界線分離了兩個蒸餾範圍。如圖1所示 ，上述之三組份系統因而展現兩個蒸餾範圍：在區域A -B 一 C— A中之蒸餾範圍1及在區域B— E—D— C—B中之 蒸餾範圍2。在蒸餾範圍1內，高沸溶劑是水，而此區域 內低的沸溶劑是TBA/水共沸混合物，中間沸溶劑是無法 以純形態分離之SB A/水共沸混合物。 爲了從整體之TBA—異丁烯設備中排出 SBA，基於 此一目的，最經濟的是使用最富含S B A的股流。然而， 在TBA解離中所得之股流具有相當低的SBA含量。通常 ’此等是具有位於蒸餾範圍1內之組成份。這些股流也經 常會進一步包含少量之額外物質，然而在本文中並不需要 考慮其存在。若嘗試藉由蒸餾來處理此具有蒸餾範圍1內 之組成份的混合物，則可能會離析出高沸溶劑的純水及做 爲頂部餾份之SBA/TBA/水混合物，或者在蒸餾塔之餾出 液中可能會得到最低沸點混合物之TBA/水共沸混合物， 並且在底部會獲得具有高水含量之含有SB A/TBA/水的較 高沸點混合物。因此，爲了質量平衡之理由也因爲不利的 (4) (4)200424158 蒸餾線位置，SBA含量不可充份地增加才能讓排出此一股 流在經濟上變得可行。對於分離組份或增加彼等濃度而言 ，該系統化中之互溶間隙（參考圖1 : C — F — G — C )也 沒有經濟上用途。 然而，令人驚訝地頃發現到，當TB A係以即將獲得 之混合物具有位於蒸餾範圍2之組成份的量加入於做爲進 料混合物的生產股流時，該混合物就可藉由蒸餾而分離成 SBA及TBA/水混合物。如此，SBA就可從含有水、SBA 及T B A之生產股流（其組成份係位於蒸餾範圍1的區域 內），特別是富含SBA的生產股流中分離，同時實質上 不會損失TBA。 【發明內容】 據此，本發明係提供一種可從含有S B A、T B A及水 之工業用混合物中分離S B A的方法，其中該混合物之水 的質量比例係大於接連兩個共沸混合物TBA/水及SBA/水 之蒸餾分界線的極限濃度，也就是說該混合物之 SBA/TBA/水組成份係位於蒸餾範圍1的區域內；其中係 藉由在該混合物內加入TBA至此一程度以減低水濃度， 即所得之混合物以 SB A/TB A/水之組成份來看時將具有水 的質量比例小於該接連兩個共沸混合物TBA/水及SBA/水 之蒸餾分界線的極限濃度，也就是說，依據SBA/TBA/水 組成份來看，是位在蒸餾範圍2之區域內；隨後藉由蒸餾 將此混合物分離成一含SBA之股流及一主要地含TBA和 (5) (5)200424158 水之股流。 因此，在本發明中係藉由將一含T B A股流加到一混 合物（以SBA/TBA/水之組成份來看，其係在蒸餾範圍1 內）至此一程度，即結果該三組份系統S B A / T B A /水之組 成份會位移到蒸餾範圍2，隨後再蒸餾，即可從此混合物 中分離出SBA。 本發明之方法可使從含有SBA、TBA及水之混合物 (其中水的質量比例是大於接連兩個共沸混合物TBA/水 及S B A /水之蒸餾分界線的極限濃度）中分離s B A變得可 行，因爲彼等是無法經由蒸餾而完全地分離。利用一較佳 地含有小於1 2質量％水及可能地小量高沸溶物（如藉使 異丁烯寡聚化所形成之C8-或C12 —烴類，C8 -醇類）及/ 或少量低沸溶物（如異丁烯或其他C4 -烴類）之含TBA 股流來改變混合物之濃度時，允許使用夾帶劑或其他外來 物質使分配其中，如此將可免掉排除這些輔助劑的昂貴花 費，並且在處理期間也不會使產物有受到這些輔助劑污染 的風險。此TBA股流較佳地係從一供製備無水TBA之設 備中取得。 【實施方式】 本發明之方法將如下文解說，但並不受這些具體實施 例所限制。 在本發明之從含有2 —丁醇（SBA )、三級丁醇（ TB A )及水之工業用混合物（其水的質量比例是大於接連 (6) (6)200424158 兩個共沸混合物TBA/水及SBA/水之蒸餾分界線的極限濃 度’也就是說，從SBA/TBA/水組成份來看’是位在蒸餾 範圍1內）中分離2— 丁醇（SBA)的方法中，係藉由在 該混合物中加入TB A至此一程度以減低水濃度，即所得 ~ 之混合物以SB A/TBA/水之組成份來看時將具有水的質量 比例小於該接連兩個共沸混合物TBA/水及SB A/水之蒸餾 分界線的極限濃度，也就是說，依 SBA/TBA/水組成份來 看’是位在蒸餾範圍2之區域內，隨後藉由蒸餾將此混合 φ 物分離成一含SBA之股流及一含TBA和水之股流。 較爲人喜歡地係加入一具有水含量小於1 2質量％， 較佳地小於1 0質量％，更佳地小於5質量％之含TB A股 流。此含TBA股流可包含90至99.99% TBA。除了 TBA 及可能之水外，此含TBA股流同時也可能地含有小量（ 0· 0 0 0 1至5質量％)高沸溶物（藉使異丁烯寡聚化所形成 之C8 —或C12 -烴類，C8 -醇類）及/或低沸溶物（如異丁 烯或其他C4 —烴類）。 _ 較有利的是，在加入該含TBA股流之前可先藉由蒸 餾從該工業用混合物中除去水。蒸餾該工業用混合物時可 - 分離成富含水之底部產物及具有水含量雖然大於接連兩個 ， 共沸混合物TBA/水及SBA/水之蒸餾分界線的極限濃度（ 也就是說以其SB A/ TBA/水組成份來看，係位於蒸餾範圍 1之區域內），但卻低於原始之水濃度的頂部產物。然後 ，根據本發明藉由加入一含TB A股流以便處理該已依此 方式預處理之工業用混合物。此一步驟的優點是，只要加 (7) (7)200424158 入相當少量的含TB A股流，就可改變混合物之濃度使之 位於蒸I留範圍2的區域內。 已加入含T B A股流且已藉由蒸餾處理之混合物較佳 地具有小於1 0質量％ (相對於三組份系統SB A/TB A/水） 的水含量。然而，更重要的是，以其水含量來看，該混合 物是處於蒸餾範圍2內，也就是說，彼具有的水質量比例 係小於那些組成份是相對應於連接共沸混合物TBA/水及 SB A/水之蒸餾分界線B - C的混合物之水含量。在SB A 含量爲0.0 00 1至6質量％下，相對於三組份系統 SBA/TBA/水的水含量最好是小於π質量％，較佳地小於 1 0質量％，更佳地小於9 · 5質量％。在S B A含量爲6.0 1 至15質量％下，相對於三組份系統SBA/TBA/水的水含量 較佳地小於1 5質量％，更佳地小於1 4質量％，特別佳地 是小於1 3質量％。除此之外，此混合物可進一步包含高 至5質量％ ’較佳地高至3質量％，更佳地2 · 5至〇 · 〇 1質 量％的額外物質，如C 8 -烯烴或C 8 -醇類。 在本發明之方法中，該已加入含TBA股流之混合物 較佳地係經由分餾，以獲得含有小於1質量％，較佳地小 於0.5質量％三級丁醇的含2 -丁醇餾份。欲藉由蒸餾處 理來分離之2 - 丁醇可從蒸餾塔中的汽化器以氣相方式或 在此塔之汽提區中以氣態或液態側流形式取走。 在進行該已加入含TB A股流之混合物的分篇作用中 ，以餾出液獲得之頂部產物有至少一部份可與該已加A含 TB A股流之工業用混合物混合。端視工業用混合物之起初 (8) (8)200424158 濃度及經由蒸餾除去水而定，此三組份混合物可具有在蒸 餾分界線B - C附近之濃度。在此一組成份的情況下，只 要小量的含TB A股流與在塔頂部獲得之餾出液產物中的 一部份組合，再一起加入工業用混合物，就已相當足夠了 ，因爲混合物之組成份也可依此方式位移到蒸餾範圍2內 〇 依本發明之方法所得的股流，特別是該已加入含TB A 股流之混合物，其分餾作用可在一或多個供應有塔盤、旋 轉式內部構件、無規塡裝元件及/或有序之塡裝元件等內 部構件的蒸餾塔中進行。而此混合物以蒸餾來分離時，較 佳地係在單一個蒸態塔中進行。 在塔盤之情況中，可使用下列形式： 金屬板內具有洞或隙縫之塔盤； 具有經帽舌、帽罩或蓬蓋覆蓋之頸狀物或煙囪狀物的 塔盤； 金屬板內具有被可移動閥蓋住之洞的塔盤； 具有特殊構件之塔盤。 在具有旋轉式內部構件之蒸餾塔中，回流可藉由旋轉 漏斗來噴灑或是藉由轉子以薄膜方式灑在一加熱管上來噴 灑。 具有各種裝塡元件之不規則床可應用於本發明方法所 用之蒸態塔內。彼等實質上可由多種材料所製成，例如鋼 、不鏡鋼、銅、碳、石製品、磁料、塑料等，同時也可具 有各種形狀，如球形、具有平坦或縱斷面之環、具有內在 -11 . (9) (9)200424158 網狀物或壁上有洞之環、金屬絲網環狀物、鞍狀、螺旋形 〇 舉例之，具有正規幾何圖形之裝塡元件可包括由金屬 或塑料製品製成之薄板狀物或梭織之網狀物。此類裝塡元 件之實例包括由薄板金屬製成之Sulzer Gewebepackungen BX、 Sulzer Lamellenpackungen Mellapak，高个生會§ 裝塡元 件如M e 11 a p a k P 1 u s、取自S u 1 z e r公司之結構性裝塡元件（ Optiflo w ) 、Μ ο n t z ( SBH)及 Kuehni ( Rombopak)。 用來使工業用混合物（其係做爲起始物質）初步脫水 之蒸餾塔（2 )較佳地具有3至5 0個理想板，更佳地6至 4 0個理想板。流入板之數目端視在蒸餾範圍1之混合物 的組成份而定。較佳地進料係從頂部算起第2個至第5 5 個理想板上導入，更佳地係在第3至第3 5個理想板。 用來分離該經由加入含TBA股流所獲得之混合物的 塔較佳地具有5至7 0個理想板，更佳地1 〇至6 0個理想 板。流入板之數目端視該混合物之組成份而定。頃發現， 對該混合物較有利的是將進料從頂部算起之第2個至第 5 5個理想板上導入’更佳地係在第3至第3 5個理想板。 蒸餾塔（2 )及（6 )之運轉壓力較佳地係〇. 〇 1至j 5 巴絕對彳直（巴拉（bara ))。在工業用混合物加入含 TBA 股流之前該用來從中除去水的塔（預備性蒸餾塔）及該用 來分餾該已加入含TB A股流後所得之混合物的塔可在相 同或各異的壓力下操作。在壓力是相同的例子中，蒸餾塔 係在〇. 5至1 0巴下操作，然而在不同壓力的例子中，預 -12 - (10) (10)200424158 備性蒸餾塔較佳地係在0 · 5至1 0巴拉範圍內，而塔（6 ) 則較佳地係在0.1至1 0巴拉的範圍內。 使該經由加入含TBA股流而獲得之混合物進行蒸餾 ，可得到含有2 - 丁醇及可能地高沸溶物之底部產物。此 一股流之T B A含量較佳地係小於2質量％，更佳地小於 1 · 7質量％。具有TB A、水及任何低沸溶物之混合物可在 頂部獲得。頂部產物之2 -丁醇含量較佳地係小於4質量 %，更佳地小於3質量％。不含或實質上不含高沸溶物之 2 —丁醇可經由從汽化器以蒸氣相方式或從塔之汽提區以 氣態或液態側流形成取走而製得。 藉由本發明方法從混合物中分離之TB A餾份可應用 於已知之目的上。舉例之，彼等可充當爲製備異丁烯之起 始物質。其內存在之任何低沸溶物可經由蒸餾移除。 已分離之2 -丁醇可利用於慣常之工業應用上。舉例 之’彼可用做爲甲基乙基酮之前驅物，表面塗料及樹脂之 溶劑，煞車油之成份及淸潔劑成份。再者，彼也使用於芳 香劑、染料及潤滑劑之製造上。 本發明之方法可使2 — 丁醇從任一含有TB A、SB A及 水且位於蒸餾範圍1內之三級混合物中分離，且不會損失 TB A。縱使此混合物進一步含有高至5質量％之高沸溶物 (如箱使異丁烯寡聚化而生成之C8 —或C12 -烴類、C8 一醇類）及/或低沸溶物（如異丁烯或其他c 4 一烴類）， 此一方法也會成功。因此，可藉由本發明之方法來製備2 一丁醇’特別是含有小於1質量％，較佳地小於〇 · 5質量 -13 ~ (11) (11)200424158 %之三級丁醇含量的2 - 丁醇。 特定言之’取自其中係藉由脫水反應以便從TB A中 製得異丁烯之工廠設備中的富含2 - 丁醇之TB A股流可應 用本發明之方法。通常，此類股流可進一步包括C4 -烴 類及可做爲額外組份之C4 -烯烴下游產物。 可進行本發明方法之特定具體實施例的設備之方框圖 係顯示於圖2中。充當爲起始進料之工業用混合物（1 ) (其具有在蒸餾範圍1之組成份）將先在塔（2 )(也可 稱爲預備性蒸餾塔）中處理，依此，一富含水之股流（3 )就可在此預備性蒸餾塔之底部卸下。然後，以能使該所 得之混合物具有位於蒸餾範圍2內之組成份的量將一含 TB A股流（5 )加入於已依此方式部份脫水但仍具有在蒸 餾範圍1內之組成份的工業用混合物（4 )中。若需要時 ，可再將取自塔（6 )之餾出液（8 )的一部份（9 )加入 於此混合物中，但須以加入後不會改變組成份使不再位於 蒸餾範圍2內的量來添加。將此一混合物送入塔（6 )中 ，依此就可分離出含有欲被析出之2 -丁醇的底部產物（ 7 )及含有TB A、水及可能地低沸溶物之頂部產物（8 )。 所有或部份的餾出液股流（8 )可直接再利用爲TBA解離 作用之進料。塔（6 )可選擇地係在不同於塔（2 )之壓力 下操作。爲了獲得具有低含量之高沸溶物的2 -丁醇，此 產物可從汽化器以蒸氣相方式，或從塔（6 )之汽提區域 中以氣態或液態側流（7A )之形式取走。 爲了以最簡單的變數來操作本發明之方法，可省略塔 -14 - (12) (12)200424158 (2 )，並以能使該混合物之組成份在蒸餾範園2的量將 含TB A股流（5 )直接加入於工業用混合物中。此股流可 在送入塔（6 )之前再次地視需要與股流（9 )混合，然後 如上述般處理。 慣用之組件，如泵、壓縮機、閥、熱交換器及汽化器 並未顯現於此方框圖中，但當然地，彼等也是屬於設備中 之組件。 下列之實施例係解說本發明，但不用來限制本發明之 範圍，本發明之範圍乃如本發明之說明及申請專利範g所 定義。 實施例 在如圖2所不之設備形態中分離S B A，但省略掉股流 (7A)及（9)。塔（2)之直徑爲50n m，且安裝著具有 1 2個理想板之金屬蒸飽塡裝元件，進料係從頂部算起的 第7個理想板上導入。同樣地，塔（6 )之直徑也爲50nm 。其內也安裝著具有20個理想板之金屬蒸餾塡裝元件， 進料係從頂部算起的第6個理想板上導入。從工業設備中 移走進料（1 )並使用在本實驗上。下表1之股流編號乃 和圖2者相同。收集來自塔（2 )之餾出液（4 )，並將部 份使用做爲第二個塔（6 )之進料。一般而言，此混合物 中濃度低於〇. 1質量份之組份將不列於該表格中。 -15 - (13)200424158 股流編號 股流名稱 質量流量 [公斤/小時] 股流之組成份質量份 1 新鮮進料 1.80 水 63.5 TBA30.2 2— 丁醇 4.5 C8 —醇 1.7 其他組份〇」 3 廢水 1.03 水 96.9 TBA0.1 2 —丁醇 0.1 C8-醇 2.9 4 脫水混合物 取自塔(2)之餾出液 0.77 水 18.9 TBA70.3 2 —丁醇 10.4 C8 —醇 0·1 其他組份0.3 4 脫水混合物 導入塔(6)之進料 0.75 水 18.9 ΤΒΑ70.3 2— 丁醇 10.4 C8 —醇 0.1 其他組份0.3 5 新鮮之TBA 0.75 水 0.004 ΤΒΑ99.8 2— 丁醇 0.15 C8 —醇 0.01 其他組份0.036 7 來自塔⑹之 底部產物 0.08 ΤΒΑ0.3 2— 丁醇 96.7 C8 —醇 1.2 其他組份1.9 7A 來自塔⑹之 可取走的側流 省略 8 來自塔⑹之 餾出液 1.42 水]0.0 ΤΒΑ89.6 2 —丁醇 0.4 其他組份0.1 9 再循環股流 省略 -16 - (14) (14)200424158 塔（2 )係在1巴絕對値下操作，且回流比爲3 .5。塔 (6 )係在1巴絕對値下操作，且回流比爲4。 從表1中可看出，本發明之方法可使依簡單方式分離 出SBA變得可行，並且可使塔頂部獲得之產物中TBA的 損失限制在很小之比例。 【圖式簡單說明】 圖1係顯示一含有TBA、SBA及水之三組份系統的 圖。 圖2係顯示一可進行本發明方法之特定具體實施例之 設備的方框圖。 元件對照表 1 : 工業用混合物 2 ·* 蒸餾塔 3 :富含水之股流 φ 4 :工業用混合物之餾出液 5 : 含TBA股流 ， 6 : 塔 _ 7 :底部產物 7A : 側流 8 :頂部產物（餾出液股流） 9 : 餾出液（8 )之一部份 -17 -Therefore, the object of the present invention is to provide a method capable of separating SBA from a mixture containing SB A, TBA (3) (3) 200424158 and water without TBA loss. However, the three-component SBA 'mixture of TBA and water is difficult to separate by distillation' because the three-component system shows the steamer crane demarcation line 'which is connected to about 11% by weight of water (the literature reports that it is at atmospheric pressure 10 to 1 2.5% by weight) of two components of water / TB A azeotrope (point B in Figure 1), and at about 28% by weight of water (literature reports are at atmospheric pressure 2 6 · 7 to 3 2 Water / SBA azeotrope (point C in Fig. 1), the second component of the water by weight. This distillation boundary separates two distillation ranges. As shown in Figure 1, the three-component system described above thus exhibits two distillation ranges: Distillation range 1 in regions A-B-C-A and Distillation range 2 in regions B-E-D-C-B . In the distillation range 1, the high-boiling solvent is water, while the low-boiling solvent in this region is a TBA / water azeotrope, and the middle-boiling solvent is a SBA / water azeotrope that cannot be separated in pure form. In order to discharge SBA from the overall TBA-isobutylene plant, for this purpose, it is most economical to use the stream that is richest in SBA. However, the stream obtained during TBA dissociation has a relatively low SBA content. Usually, these are components having a composition within the distillation range 1. These streams often also contain small amounts of additional substances, but their presence need not be considered in this article. If you try to treat this mixture with components in the distillation range 1 by distillation, pure water with high boiling solvent and SBA / TBA / water mixture as the top fraction may be isolated, or distillation in the distillation column A TBA / water azeotropic mixture with the lowest boiling point mixture may be obtained in the effluent, and a higher boiling point mixture containing SB A / TBA / water with a high water content may be obtained at the bottom. Therefore, for reasons of mass balance and because of unfavorable (4) (4) 200424158 distillation line positions, the SBA content cannot be increased sufficiently to make it economically feasible to discharge this stream. For separating components or increasing their concentrations, the intermiscibility gap in the system (refer to Figure 1: C — F — G — C) is also not economically useful. However, it was surprisingly found that when TBA is added to the production stream as a feed mixture in an amount that the mixture to be obtained has a composition in the distillation range 2, the mixture can be obtained by distillation. Separated into SBA and TBA / water mixture. In this way, SBA can be separated from production streams containing water, SBA, and TB A (their constituents are located in the distillation range 1 area), especially SBA-rich production streams, without substantial loss of TBA. SUMMARY OF THE INVENTION Accordingly, the present invention provides a method for separating SBA from an industrial mixture containing SBA, TBA, and water, wherein the mass ratio of water in the mixture is greater than two consecutive azeotropic mixtures TBA / water and The limit concentration of the distillation boundary of SBA / water, that is, the SBA / TBA / water composition of the mixture is located in the region of the distillation range 1; in which TBA is added to the mixture to this extent to reduce the water concentration That is, when the obtained mixture is viewed in terms of the composition of SB A / TB A / water, the mass ratio of water will be less than the limit concentration of the distillation boundary between the two azeotropic mixtures TBA / water and SBA / water, that is, That is, according to the SBA / TBA / water composition, it is located in the region of the distillation range 2; the mixture is then separated by distillation into a stream containing SBA and a stream containing mainly TBA and (5) (5) 200424158 The stream of water. Therefore, in the present invention, by adding a TBA-containing stream to a mixture (in terms of the composition of SBA / TBA / water, which is within the distillation range 1) to the extent that the three components result The components of the system SBA / TBA / water are shifted to the distillation range 2 and subsequently distilled to separate the SBA from this mixture. The method of the present invention can separate s BA from a mixture containing SBA, TBA and water (wherein the mass ratio of water is greater than the limit concentration of the distillation boundary of two consecutive azeotropic mixtures TBA / water and SBA / water). It works because they cannot be completely separated by distillation. Utilizing a preferably containing less than 12% by mass of water and possibly a small amount of high-boiling solubles (such as C8- or C12-hydrocarbons, C8-alcohols formed by isobutene oligomerization) and / or a small amount of low-boiling When the TBA-containing stream of substances (such as isobutylene or other C4-hydrocarbons) is used to change the concentration of the mixture, it is allowed to use an entrainer or other foreign substances to distribute it. This will avoid the expensive cost of excluding these auxiliary agents, and The product is also not at risk of contamination by these adjuvants during processing. This TBA stream is preferably obtained from a facility for preparing anhydrous TBA. [Embodiment] The method of the present invention will be explained below, but it is not limited by these specific examples. In the present invention, an industrial mixture containing 2-butanol (SBA), tertiary butanol (TB A) and water (the mass ratio of water is greater than that of consecutive (6) (6) 200424158 two azeotropic mixtures TBA The limiting concentration of the distillation boundary of water / water and SBA / water 'that is, from the perspective of SBA / TBA / water composition' is in the distillation range 1) method of separating 2-butanol (SBA), By adding TBA to this level to reduce the water concentration, that is to say, the obtained mixture will have a mass ratio of water less than the two consecutive azeotropic mixtures when viewed from the SB A / TBA / water composition. The limiting concentration of the distillation boundary of TBA / water and SB A / water, that is, the SBA / TBA / water composition is considered to be in the region of the distillation range 2 and then the mixture is distilled by distillation. Separate into a stream containing SBA and a stream containing TBA and water. It is preferred to add a TB-containing A stream having a water content of less than 12% by mass, preferably less than 10% by mass, and more preferably less than 5% by mass. This TBA-containing stream can contain 90 to 99.99% TBA. In addition to TBA and possible water, this TBA-containing stream may also contain small amounts (0 · 0 0 0 1 to 5% by mass) of high-boiling solubles (C8 — or C12 — hydrocarbons formed by oligomerization of isobutylene). Class, C8-alcohols) and / or low boiling matter (such as isobutylene or other C4-hydrocarbons). _ Advantageously, water can be removed from the industrial mixture by distillation before adding the TBA-containing stream. When distilling this industrial mixture, it can be-separated into a water-rich bottom product and having a water content greater than two consecutive, the limit concentration of the distillation boundary of the azeotropic mixture TBA / water and SBA / water (that is, its SB A / TBA / water composition, the top product is located in the distillation range 1), but it is lower than the original water concentration. Then, according to the present invention, the industrial mixture which has been pretreated in this manner is treated by adding a stream containing TB A. The advantage of this step is that as long as (7) (7) 200424158 is added to a relatively small amount of TB-containing A stream, the concentration of the mixture can be changed so that it lies within the region of steam retention range 2. The mixture containing the T B A stream and which has been treated by distillation preferably has a water content of less than 10% by mass (relative to the three-component system SB A / TB A / water). However, more importantly, in terms of its water content, the mixture is in the distillation range2, that is, it has a water mass ratio smaller than those components that correspond to the connected azeotropic mixture TBA / water and SB A / Water Distillation B-C mixture water content. At a content of SB A of 0.0 00 1 to 6% by mass, the water content of SBA / TBA / water relative to the three-component system is preferably less than π% by mass, preferably less than 10% by mass, and more preferably less than 9 5 mass%. At an SBA content of 6.0 1 to 15% by mass, the water content of the SBA / TBA / water relative to the three-component system is preferably less than 15% by mass, more preferably less than 14% by mass, and particularly preferably less than 1 3% by mass. In addition, this mixture may further contain up to 5% by mass' preferably up to 3% by mass, more preferably 2.5 to 0.001% by mass of additional substances, such as C 8 -olefins or C 8 -Alcohols. In the method of the present invention, the TBA-containing stream that has been added is preferably fractionated to obtain a 2-butanol-containing fraction containing less than 1% by mass, preferably less than 0.5% by mass of tertiary butanol. . The 2-butanol to be separated by distillation can be removed from the vaporizer in the distillation column in the gas phase or in the stripping zone of the column as a gaseous or liquid side stream. In performing the sectioning of the mixture containing the TB A-containing stream, at least a part of the top product obtained from the distillate can be mixed with the industrial mixture containing the TB A-containing stream having been added. Depending on the initial concentration of the industrial mixture (8) (8) 200424158 and the removal of water by distillation, the three-component mixture may have a concentration near the distillation boundary line B-C. In the case of this group of ingredients, as long as a small amount of TB-containing A stream is combined with a part of the distillate product obtained at the top of the column, and then added to the industrial mixture, it is quite sufficient, because the mixture The constituents can also be shifted to the distillation range 2 in this way. The strands obtained according to the method of the present invention, especially the mixture to which the TB A-containing stream has been added, can be fractionated by one or more towers. It is carried out in a distillation column with internal components such as pans, rotating internal components, random outfitting elements and / or ordered outfitting elements. When this mixture is separated by distillation, it is preferably carried out in a single distillation column. In the case of a tray, the following forms can be used: A tray with holes or gaps in a metal plate; a tray with a neck or chimney covered by a tongue, cap or canopy; a metal plate with Tray with holes covered by removable valves; trays with special components. In a distillation column with rotating internals, the reflux can be sprayed by a rotating funnel or sprayed on a heating tube in a thin film by a rotor. Irregular beds with various decoration elements can be used in the steam column used in the method of the present invention. They can be made of a variety of materials, such as steel, stainless steel, copper, carbon, stone products, magnetic materials, plastics, etc., and can also have various shapes, such as spherical, ring with flat or vertical section, Has inner -11. (9) (9) 200424158 Rings with holes in the mesh or wall, metal mesh rings, saddles, spirals. For example, a decoration element with a regular geometry may include Sheet metal or woven mesh made of metal or plastic. Examples of such decoration elements include Sulzer Gewebepackungen BX, Sulzer Lamellenpackungen Mellapak, made of sheet metal, high society members § decoration elements such as Me 11 apak P 1 us, structural equipment from Su 1 zer Plutonium elements (Optiflo w), M ntz (SBH) and Kuehni (Rombopak). The distillation column (2) used for the preliminary dehydration of the industrial mixture (which is used as the starting material) preferably has 3 to 50 ideal plates, and more preferably 6 to 40 ideal plates. The number of inflow plates depends on the composition of the mixture in the distillation range 1. Preferably, the feed is introduced from the top to the 2nd to 5th ideal plates from the top, and more preferably to the 3rd to 35th ideal plates. The column used to separate the mixture obtained by adding the TBA-containing stream preferably has 5 to 70 ideal plates, more preferably 10 to 60 ideal plates. The number of inflow plates depends on the composition of the mixture. It was found that it is more advantageous for the mixture to introduce the feed from the second to the 55th ideal plate from the top, and more preferably to the 3rd to the 35th ideal plate. The operating pressures of the distillation columns (2) and (6) are preferably from 0.01 to 5 bar absolutely straight (bara). The column (preliminary distillation column) used to remove water before the TBA-containing stream is added to the industrial mixture and the column used to fractionate the mixture obtained after adding the TBA-containing stream may be the same or different. Operate under pressure. In the case where the pressures are the same, the distillation column is operated at 0.5 to 10 bar. However, in the case of different pressures, the pre-12-(10) (10) 200424158 preparative distillation column is preferably connected at In the range of 0.5 · 10 to 10 Barra, the tower (6) is preferably in the range of 0.1 to 10 Barra. Distilling the mixture obtained by adding a TBA-containing stream, a bottom product containing 2-butanol and possibly a high boiling point can be obtained. The T B A content of this stream is preferably less than 2% by mass, and more preferably less than 1.7% by mass. Mixtures with TB A, water and any low-boiling solubles are available at the top. The 2-butanol content of the top product is preferably less than 4% by mass, and more preferably less than 3% by mass. 2-butanol, which contains no or substantially no high-boiling solubles, can be prepared by removing it as a vapor phase from the vaporizer or as a gaseous or liquid side stream from the stripping zone of the column. The TBA fraction separated from the mixture by the method of the present invention can be used for a known purpose. For example, they can serve as starting materials for the preparation of isobutylene. Any low boiling solids present in it can be removed by distillation. The isolated 2-butanol can be used in customary industrial applications. For example, it can be used as a methyl ethyl ketone precursor, a solvent for surface coatings and resins, a component of brake oil, and a detergent component. Furthermore, it is also used in the manufacture of fragrances, dyes and lubricants. The method of the present invention allows 2-butanol to be separated from any tertiary mixture containing TB A, SB A and water and located within the distillation range 1 without loss of TB A. Even if this mixture further contains up to 5% by mass of high boiling matter (such as C8 — or C12 — hydrocarbons, C8 alcohols produced by oligomerization of isobutene in a box) and / or low boiling matter (such as isobutene or other c 4 a hydrocarbon), this method will also be successful. Therefore, 2 monobutanol 'can be prepared by the method of the present invention, especially 2 containing tertiary butanol content of less than 1% by mass, and preferably less than 0.5 mass -13 ~ (11) (11) 200424158%. -Butanol. In particular, taken from a 2-butanol-rich TB A stream in a plant where the dehydration reaction is used to produce isobutene from TB A, the method of the present invention can be applied. Generally, such streams may further include C4-hydrocarbons and C4-olefin downstream products that may be used as additional components. A block diagram of a device that can perform a particular embodiment of the method of the present invention is shown in FIG. The industrial mixture (1) (which has a composition in the distillation range 1) serving as a starting feed will first be processed in a column (2) (also known as a preliminary distillation column), and accordingly, a rich The water stream (3) can be unloaded at the bottom of this preliminary distillation column. Then, a TB-containing A stream (5) is added to the composition which has the composition within the distillation range 2 in such an amount that the obtained mixture has the composition which has been partially dehydrated in this manner but still has the composition within the distillation range 1. Industrial mixture (4). If necessary, a part (9) of the distillate (8) from the column (6) can be added to the mixture, but the composition will not be changed so that it is no longer in the distillation range 2 Within the amount to add. This mixture is sent to the column (6), whereby the bottom product (7) containing 2-butanol to be precipitated and the top product (TBA, water, and possibly low-boiling solubles) can be separated ( 8 ). All or part of the distillate stream (8) can be directly reused as feed for TBA dissociation. The tower (6) can optionally be operated at a pressure different from that of the tower (2). In order to obtain 2-butanol with a low content of high boiling matter, this product can be removed from the vaporizer as a vapor phase, or as a gaseous or liquid side stream (7A) from the stripping zone of the column (6). In order to operate the method of the present invention with the simplest variables, columns -14-(12) (12) 200424158 (2) can be omitted, and TB A will be included in an amount that enables the composition of the mixture to be distilled in the range 2 The stream (5) is added directly to the industrial mixture. This stream can be mixed with the stream (9) again as needed before being sent to the tower (6) and then processed as described above. Conventional components such as pumps, compressors, valves, heat exchangers and vaporizers are not shown in this block diagram, but of course they are also components in the equipment. The following examples are illustrative of the present invention, but are not intended to limit the scope of the present invention. The scope of the present invention is defined by the description of the present invention and the patent application g. Example Separate S B A in the equipment form shown in Fig. 2, but omit the streams (7A) and (9). The tower (2) has a diameter of 50 nm and is equipped with metal steam-saturated outfitting elements with 12 ideal plates. The feed is introduced from the 7th ideal plate from the top. Similarly, the diameter of the tower (6) is also 50 nm. There are also metal distillation outfitting elements with 20 ideal plates, and the feed is introduced from the 6th ideal plate from the top. The material (1) was removed from the industrial equipment and used in this experiment. The flow numbers in Table 1 below are the same as those in Figure 2. The distillate (4) from the column (2) is collected and used partly as feed for the second column (6). In general, components with a concentration of less than 0.1 parts by mass in this mixture will not be listed in the table. -15-(13) 200424158 Stream number Stream name Mass flow [kg / hour] Composition of stream 1 Mass feed 1 1.80 Water 63.5 TBA30.2 2—Butanol 4.5 C8—Alcohol 1.7 Other components 〇 '' 3 Wastewater 1.03 Water 96.9 TBA0.1 2-butanol 0.1 C8-alcohol 2.9 4 Dehydrated mixture Distillate from column (2) 0.77 Water 18.9 TBA70.3 2 -butanol 10.4 C8-alcohol 0 · 1 Other groups 0.34 parts of the dehydrated mixture introduced into the tower (6) feed 0.75 water 18.9 TBA70.3 2-butanol 10.4 C8-alcohol 0.1 other components 0.3 5 fresh TBA 0.75 water 0.004 TBA 99.8 2-butanol 0.15 C8-alcohol 0.01 Other components 0.036 7 Product from the bottom of the tower. 0.08 TBA 0.3 2-Butanol 96.7 C8-Alcohol 1.2 Other components 1.9 7A Removable side flow from the tower. Omitted 8 Distillate from the tower. 1.42 Water] 0.0 ΤΒΑ89.6 2 -butanol 0.4 Other components 0.1 9 Recirculation stream omitted -16-(14) (14) 200424158 Tower (2) is operated at 1 bar absolute pressure, and the reflux ratio is 3. 5. The tower (6) is operated at an absolute pressure of 1 bar and the reflux ratio is 4. As can be seen from Table 1, the method of the present invention makes it possible to separate SBA in a simple manner, and limits the loss of TBA in the product obtained at the top of the column to a small proportion. [Brief description of the figure] Figure 1 is a diagram showing a three-component system containing TBA, SBA and water. Fig. 2 is a block diagram showing an apparatus which can carry out a specific embodiment of the method of the present invention. Component comparison table 1: Industrial mixture 2 * Distillation column 3: Water-rich stream φ 4: Industrial mixture distillate 5: TBA-containing stream, 6: Column_7: Bottom product 7A: Side stream 8: top product (distillate stream) 9: part of distillate (8) -17-